TW575699B - Low pressure vapor phase deposition of organic thin films - Google Patents

Description

575699 V. Description of the invention (l) ---------- US government ^^ The present invention is supported by 1 _ τ Αη Government of the poor country, contract number F49620-92- J-05 24 6, Room) University of Houston), the United States Air Force 〇SR (Science and Technology Research Office to the United States Government has certain rights to the invention. Scope of the invention ^ The invention relates to the manufacturing method of optical quality films, especially for non-linear optics Devices and organic light-emitting devices such as low-voltage manufacturing methods of thin films. JL bright background, organic electricity% luminescence is a fast-growing technology, and is being stimulated because it is considered a potential display device. Organic light-emitting devices (OLEDs ) Can achieve an additional 3% quantum efficiency, and the service life under visual brightness can reach the level of 10,000 hours. At present, both small molecules and plastic substrates are known, but polymers The substrate device has the advantages of simplicity and cheapness due to the use of rotary deposition technology. In contrast, vacuum thermal evaporation is usually used to manufacture small molecular devices. The manufacturing cost is higher than that of rotary deposition technology. ED structure and manufacturing technology No. ㈣96 / 19 ~ 92, which is referred to in this article, has been provided. ~ The use of organic vapor vapor deposition (0VPD) has been advanced to use in many and small photovoltaic devices such as display devices. Low-cost ^ size deposition, the 0VPD method is referred to herein as US Patent No. 5: '5 54'220, fortified by Forrest et al .; SR Forrest et al. Second harmonic generation ~ long-distance structure order "68 Appl. Phys. Lett.i 326 (1 9 9 6).

苐 Page 575699 Description of the Invention (2) —— and PF r ^ · bUrrows et al. "Organic Vapor Deposition: A New Method for the Formation of Organic Films with High Optics and Reactivity, 156 j. 〇f crystal Growth 9 1 (199 5) are all detailed. The PD method enables the carrier gas to be used to transfer the raw materials to the substrate, and the gas condensation = the desired film. For example, the OVPD technology has been used for optical nonlinearity (Das salt + hydrazone). Mineral acid 4, -diamidinoamino-N-fluorenyl-4—azo | & I from the evaporable precursor monoiodized 4, -diamidinoamino-N-fluorenyl im 4 -(DASI) and p-toluene xanthanate methyl carbamate (pyroxybenzoate, n / ,, and di) are transferred from the carrier gas to the heated substrate, and at this time, they are decomposed into 4-dimethylamino groups. A 4_azo group (DAS) 'DAS reacts with MT to form DAST on the substrate. As the co-deposition of materials can be controlled under extremely different vapor-pressure conditions, 0vpD 1 ^ = The only method for forming a thin film, however, the IPVD method is used to implement the 0PVD method. The film is formed at atmospheric pressure or near atmospheric pressure due to gas-phase nucleation and diffusion-limited production processes. The film has a coarser sugar and uneven surface morphology. Summary of the invention The present invention provides a method and a device for generating an organic film with excellent surface area (1 shell) under subatmospheric pressure. The present invention includes a method for preparing an organic thin film on a substrate. The it method includes the following steps: Extraction two: ί organic precursors, and the precursors are in a vapor phase state; 纟 in the sub-atmosphere = /, sub-under a substrate Various precursors react to form a thin film on the substrate. On the other hand, the present invention includes a thin film made by this method, and on the other hand, the present invention includes a method for promoting organic precursors under subatmospheric pressure.

575699

5. Description of the invention Device for reacting (3) substances to form an organic thin film on the surface of a substrate. An advantage of the present invention is to provide a multi-component organic thin film which can precisely control the content of each component. f Another advantage of the invention is to provide a uniform, strong and stable hair with a smooth surface. Another advantage is to provide a low-pressure organic vapor phase deposition method and set 'for generating organic light-emitting materials and optically non-linear salts. The film. Another advantage of the present invention is to provide a low-pressure organic molecular beam deposition method and apparatus' for forming a thin film of an organic light-emitting material and an optically non-linear salt. Another advantage of the present invention is to provide a method and apparatus capable of forming a uniform organic material deposition on a large substrate area. Explanation of the example-Figure 1 is a LPOVPD reaction chamber according to a specific embodiment of the present invention. FIG. 2 is a MVD reaction chamber according to a specific embodiment of the present invention. FIG. 3 shows a continuous low-pressure substrate deposition apparatus for organic materials according to an embodiment of the present invention. . 4A and 4B are a plan view and a cross-sectional view, respectively, of a reaction gas dispersion kit according to a specific embodiment of the present invention. 5 is a side view of a roller substrate conveying mechanism according to a specific embodiment of the present invention

view. DETAILED DESCRIPTION The present invention provides a method and apparatus for forming an organic thin film with excellent surface properties on a substrate under sub-atmospheric pressure. This method of the present invention is called low pressure organic vapor deposition (LPOVPD), and the LPOVPD method of the present invention Content

Page 6 575699 Sub-organic thin film with excellent implementation of roughness. It includes a reaction chamber, cylindrical and has a length of about 45 or quartz. — Put it in the round tube 36, put the pot 14 directly on it, and hang it down 1 to 4 to 18 to heat the organic precursor stream 30 to pass the drive steam along with the gas such as nitrogen gas is also an inert gas too much reactant tank 2 4 By adjusting the diameters 30 and 38, the device 3 2. The flow is transmitted to the inverter 40, and the flow is transmitted to the deposition. The LPOVPD of this example with different surface properties, such as the reaction tube 1 2 is suitable in size, and the reaction contains the first Inside and placed in the reaction tube 1 2 Use tight packing or cooling, control the material thermal decomposition of the round tube 3 6 and enter the reaction tube 1 2, helium, argon,, such as hydrogen, ammonia. 'This will have an additional throttle valve 2 6 Transfer and flow into the reaction meter 3 4 and one of the quick response tubes 12 2 and the meter 4 2 contains the second reaction chamber 10 and extends to, for example, the solid tube 1 2 can make the precursor of the machine close to the reaction or place it. Surrounding the reaction crucible 14 or sublimation, flow into the reaction chamber to the exhaust gas 氪, 氤, Ⅴ. Description of the invention (4) Allows precise control of multiple characteristics such as low surface-according to the present invention, the reaction chamber 10 The reaction tube 1 2 is 10 cm in diameter, suitable material such as broken glass Container such as a crucible 4 end station 20. In addition, the first inert carrier gas in the heating / cooling crucible 14 in the area where the partition plate or the round tube is hung; the first organic precursor carrier gas is an inert gas, and for reducing organic materials, it is The two essential gases are at least two from the gas, the soil t ^] adjusting the moving path 3 includes pressure regulation, the carrier gas includes pressure regulation every Γ, and the carrier gas passes through the outside. The film of the present invention is shown in Figure 1. The temperature of the open pipe 12 of any material used in the laboratory inspection device is as much as the temperature of the pipe 12 which makes it regulated. The end 22, inert neon, etc., and pinane, etc., are reduced to many types. Gas usually helps. Tubes 2 to 8 are transferred to tubes 1 2. One flow path speed switching valve 3 5 is 2 0 'The other flow path fast switching valve 3 9 is an organic precursor material 48 575699 V. Description of the invention (5)' --- From the 'package 4 6 is It can help the temperature control of the second organic precursor material 48. The bubbler 46 is partially immersed in the liquid bath 50 in the container 52, and the gas from the gas tank 24 passes through the second organic precursor in a bubble form. After the material 48 enters the reaction chamber 12, the round tube 54 must be maintained at a sufficiently high temperature to prevent the volatilized second organic precursor 48 from condensing again when it flows from the bubbler to the chamber. ~ 、 Ran = The amount of precursors entering the reaction tube 12 is controlled by process parameters such as temperature, carrier gas flow rate and temperature of the reactants. The LpOVpD method enables the two pressure mass flow controllers to provide accurate measurement without being pioneered. The grave pressure of the material and the chemical properties are affected, so the method allows material combinations with significantly different characteristics according to the required ratio of the produced film. The precursor gas flow can be opened and closed almost instantly using the quick-change valves 3 5 and 39. These valves direct the precursor gas flow to the reaction chamber 12 or to the bypass line (not shown), so at any time, the Different precursors flow into the reaction plumber 2 to obtain different compositions and characteristics. The valve 39 adjusts the amount of carrier gas flowing into the bubbler 46. The valves 3 5 and 39 allow rapid change of the reactants entering the reaction tube 12: Transform the physical properties and composition of the resulting film. For example, A β AB, ABCABC, ABABCAB, and ABCDABCD-type films can be generated, where each letter represents a different molecular layer or composition. The vacuum pump 66 and the control throttle valve 68 are connected to the reverse chamber 10 at the exhaust port 62. Most of the organic vapor is not deposited on the substrate 58, but is located on the upstream of the vacuum pump 66 Trap trap 64, which contains, for example, liquid fresh gas or natural fluorocarbon oil, throttle valve 68 adjusts the pressure in the reaction chamber 10, and a suitable dynamometer is connected to the reaction chamber. This pressure gauge is provided with electronic feedback to Control throttling width 6 8 ^

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575699 5. Description of the invention (7) The pots 14 and 14N can be stacked vertically in the reaction tube 12 to handle additional precursors. Depending on the organic thin film to be deposited, one or more flow paths can be used alone. 3 0, 38, or any combination thereof to provide the necessary precursor material. The method of the present invention can be used to deposit many different organic thin films by the reaction of vapor precursors. Among them, "reaction" is considered to be that the precursor reactants form different reaction products, or the precursor materials form a donor-acceptor or Bin-host relationship. For example, according to the present invention, the following precursors are used to form a thin film of the following NL 0 materials using the reaction of the listed precursors: Thin film material First precursor Second precursor Toluenesulfonic acid 45-dimethylamino-N-methyl-4 -Azo: | (DAST) 4'- _ ^ methylamino-4-azofe (DAS)-methylazoi (MT) 4'-dimethylamino-4-methyl methanesulfonic acid Azofe (DASM) methyl methanesulfonate (MM) 4, -dimethylamino-4-azo4 (DAS) trifluoromethanesulfonic acid 4'-dimethylamino-4- Methyl couple MS: (DASM) Methyl trifluoromethanesulfonate (MfM) 4, -dimethylamino-4-azofe (DAS) Toluenesulfonic acid 4'-dimethylamino-N- Methyl-4-azoft (DAST) Methylazofc (MT) Thiol 4'-dimethylamino-4-methylazohydrazone (DASTh) Toluenesulfonic acid 4'-methoxy- 4-methylazo S (MeOST) methyl azo & (MT) 4, -methoxymethyl methyl azo fe (MeOS) tosylate 4'-dimethylamino-N-methyl -4-Azofi: (DAST) Methylazo & MT) 4'-Dimethylamino-4-methylazo i (DAS (Et) I) Toluenesulfonic acid 4'-Di Methylamino-N-methyl-4-azo (DAST) methylazo: fe (MT) 4'-dihydroxide Amino-4-methylazo: 1: (DAS (Et) OH) Toluenesulfonic acid 4'-dimethylamino-4-acetamidoazo S: (DAAST) Acetylazo (ATP) 4 '-— • Methylamino-4-Azo (DAS) Trifluoroacetic Acid Dimethylamino-4-Ethylazo Azofe (DASAf) Trifluoromethanesulfonic Acid Methyl Ester (MAf) 4' -Dimethylamino-4-azo: | (DAS)

Page 10 575699 V. Description of the invention (8) In another phase that is relatively similar to the light-emitting materials used to make OLEDs, the precursors are composed of tetrathlsferlvalene (TFF) ^ 7 ^ column (composed of the 'mixture' to form a deposit) The electro-transition complex butyl TF-TCNQ on the material. 4 I (two, two-based amino phenyl styrene)-I 咲. South (4 to the guest molecule of Gao Liujiawu ϋ ϋ two people ϋ) Diluted in the host matrix molecules to form an early luminous layer. Other guest molecules are Fan 5 radical-21Η, 23Η- 卩 phenphene (τρρ), red fluorescent dilute, dcm2, douxin ^ 4: ... The matrix achieves effective polychromatic changes = do Π c " double-layer light emission attack system by the hole transmission layer # Α α-4,4, -bis "-(biphenyl) -N-phenyl -Amine group] ^ this group ^ -NPD) or MTDATA, laminated on the light emitting layer (" EL ") such as Li 隹 ^ 1 1 base bis- (8_hydroxy4line) aluminum ((AlQ2),- 0Ph) or its combined combination, both HTL and EL are alternately formed to the desired thickness, and then additional layers are formed on the organic layer or organic materials such as trimethylindium and difluorenyl gallium are used. Metal source gold The contact layer. The device and method that the handle does not include, the present invention includes-as shown in Fig. 2, the μ to 70 'reaction chamber 70 includes a modified ultra-high vacuum chamber 71 and a Y-J wheel ( The vacuum pump is not connected to the valve 72. The typical true pressure is 10δ-1 0_U. The organic layer is deposited using reaction chamber 70. The nMvt is called organic molecular beam vapor deposition (0MVD). Although SLP0VPD and Sub-atmospheric pressure is used to deposit organic layers, the main difference is

575699 V. Description of the invention (9) Under the average molecular free phase winter, the average Π of LPOVPD is larger than the size of the reaction chamber 70, compared with the allowable shape of the injector L = t to the size of the gas reaction chamber, 0_丄 円 Straightening molecules "bundle" to the substrate, and can precisely control the thickness and purity of the cymbal disc. Come up and hold the bubbler 74 of the first precursor 75, and the bubbler 74 is placed in the two sub-packages: wrapped in the temperature control liquid bath 80. The high-purity inert carrier 7 '= # ί / bag passes the first-precursor 7 5 and takes away individual vapors through a heating tube and enters the vacuum chamber 71. In the vacuum chamber η, the precursor is made such as A but | and hits the substrate 8 5, and the substrate 8 5 is a method with a temperature control device such as a cold part inlet 8 1. I Ϊ = two 71 I optionally add at least one Knudsen or 1 "containing a second precursor 88, κ-element 86 is a uniform heating furnace two to permeate the evaporate under vacuum, for example, heating K -The Das generated by the solution of DASI or other precursors and sublimation in eight liters, and the das are simply Jane: "..." into the reaction chamber 70 '. In addition, K-element 86 can also enter? ΠΪ The gas port is used to dilute or evaporate the molecular species due to heating. Κ / ρ and / or this dilution procedure is useful, for example, by controlling the temperature of the liquid bath 80 and 86, and the carrier gas 78 to the bubbler 74. 1 ~ The main system is particularly dumped. 43 3 Start 4 2 θ Day 3 to monitor, rotate the sample carrier 90 to ensure the '1st reaction and reaction of the precursor, and the deposition of the precursor material is further controlled by a shutter 87 that can block the molecular beam 83 and 89 .

575699 V. Description of the invention (10) The pressure in the reaction chamber 70 may be u 1 7 1 and optionally include a cooling mask 9 1 to assist in maintaining the vacuum chamber and &1; re-evaporation of the precursor materials. It is better to include a partition yz to prevent the pioneers from moving from the primary material to contaminate each other. , * Ff to 70 can be equipped with many of the same accessories such as fast,, valve side through the official line of the LP0VPD reaction chamber as shown in Figure 1, the reaction chamber 70 can be installed more: components and bubblers to It is used to deposit a variety of pioneer materials on the substrate 85. To 70, it is best to include a “loading gate, 9 4”, “force gate 95, and vacuum pump 96 for sample loading, to avoid material replacement. The vacuum chamber and the device shown in FIG. 1 can be selectively modified to continuously and organically accumulate on the surface of a large-area substrate. As shown in the example of FIG. 3, the device in FIG. 3 includes multiple vacuum chambers such as a filling chamber 146, an organic Layer deposition chambers 150 and 152, contact deposition chamber 154 = and unloading chamber 1 56. For example, each deposition chamber is conveyed by the LPOVPD reaction of FIG. 1 to 10 'substrate 137 in a carousel 148, passes through the processing chamber 15, 152, 154, and 156. In the specific embodiment of FIG. 3, the processing chambers 150, 152, and U4 contain radiant heating sources 158, 160, and 162, respectively, to avoid condensation of organic vapor, although there are only two in FIG. 3 Organic layer deposition chambers 5 0 and 5 2 but additional deposition chambers can be added as required. Transfer from the loading chamber 46 to Layer> When the child storage chambers 1 50 and 15 2 and the contact deposition chamber 1 5 4 are transferred to the unloading chamber 1 5 6, the substrate 1 3 7 will first pass through an air lock (not shown) to avoid lifting the deposition chamber. The vacuum levels of 150, 1, 52, and 1 54. In the example of OLED, the deposition chambers 150 and 152 are used to deposit TPd and Ah, respectively, and the deposition chamber 154 is used to sink the Mg: Ag contact layer. The three deposition chambers 150, 152, and 54 each contain a deposition organic

Page 13 575699 V. Description of the invention (11)

" The reactant gas disperser (RGD) 108 is used, as detailed in Figures 4A and 4B ^ RGD 108 is another 'two to provide the air curtain UO' UO of the organic precursor transfer mechanism of Figure 1 and Figure 2, 120 ,, and 120 ,,,, and RGD 108 can ensure the deposition of organic precursors and organic precursors. The organic precursors are maintained on separate substrates and are accumulated on various substrates that react. RGD 108 contains In addition, the second carrier gas inlet 112 and the gas manifold 132 and the second port 122 prevent the premature condensation of the organic precursor materials. The second carrier gas inlet 114 is above rgd 08. With the dispersion plate 11 (), the first carrier gas inlet = port 1j 4 supplies a gas carrying a first organic precursor with low volatility such as MT, and the first carrier gas enters the reaction chamber through the dispersion plate. The dispersing plate 11 〇 is a mesh, glass-filled material, or a hole-like stainless steel plate, which flows through the dispersing plate 110 = the air flow is shielded by RGD 108, which makes the gas with the second organic precursor of low vapor pressure such as DAS into A flat air curtain 120, and a second carrier gas containing a second organic precursor is introduced into the air inlet 112 and To the gas manifold 132, the gas manifold 132 is a hollow tube with a row of holes 13, and the second carrier gas is supplied to the annular cavity 126 surrounding the gas manifold 132, and the second carrier gas passes through the slit 丨36 leaves RGD 108, and forms the shape of a flat air curtain. The air curtain 120 is composed of TPD vapor, the air curtain is 20, is composed of Uq3 vapor, and the air curtain 120 `` is composed of a conductive surface such as polypyrrole or an organometallic compound. If necessary, control or adjust 0LED The luminous color can be adjusted by the additional RGI of the deposition chamber 1 52) device 10 to produce an air curtain 1 20 ′ ′ ′ of dopant vapor to adjust the appropriate doping amount of the A1 q3 layer. The device of Figure 1, Figure 2 or Figure 3 can use a "roller—to_roller,"

Page 14 575699 V. Description of the invention (12) The transmission system is selectively modified. As shown in Figure 5, the unified system is suitable for large-area, elastic substrates. The transmission system shown in Figure 5 is based on polymers. It is made of plate or metal foil, and there is a machine / membrane such as base 182, and the organic precursor on the substrate 180 is deposited by the roller "I", and the roller 1 80 is separated from the roller 丨 8 i and is exposed to Figure i The reaction '77 Don't say the molecular beam or air curtain born in / substrate Figure 3; 衮 wheels 181 and 18; use ^ J Figure 2 and = black movement, such as variable speed motor, substrate 180 is transferred by roller 181 to The speed of the roller ff represents the film thickness of the organic thin film formed on the substrate 180. It is clear that the present invention is further described with reference to the following examples that are not limited to this example. Example 1 Using the device of FIG. The glass and elastic polyester substrate that have been pre-coated with indium tin (ITO) transparent layer, ιτ〇 form the electrode of the milk, the thickness of which is 1700 angstroms of glass and 1 2 0 0 ^^ : The obtained electrode impedances are 10Ω and 60Ω respectively. The glass substrate is cleaned in a ultrasonic bath with a solution of deionized water using a detergent. Then to HL, BU three gas / methane make steam bath, followed by rinsing with acetone, and finally rinse with isopropanol. In order to avoid exposure to the damage caused by the organic solvent, the detergent and the elastic substrate only in propanol rinse.,

The glass substrate is placed in the reaction tube 12 where the temperature is close to 220. The first layer > on the surface of IT 0 is the hole transporting material τ pd. Specifically, τ pd vapor is suspended from the nitrogen carrier gas. The problem 14 is carried to the substrate a, and the tpd generation conditions include: the source temperature is 2000 ± 5. (:, Nitrogen carrier gas flow rate is 100 sccm, reaction chamber pressure is 0.550 Torr and generation time is 20 minutes. Nitrogen

Page 15 575699

When the gas carrier gas flow rate is 100 sccm, its system Reynolds number is ~ 50 (). It does not work in the laminar flow area, and the thickness of the TPD layer is between 丨 ⑽_3 and 沉积. After deposition, the temperature close to the TPD hanging pot is reduced. And close related ,. Alaska, nine streams, and then opened the separated nitrogen line from the gas 14N into the reaction chamber 12 to generate an electron transport layer, the ai parts include: the source temperature is 247 ± 8t, the nitrogen carrier gas flow rate is 50 Sccm, the reaction to a pressure of 0.65 Torr and a generation time of 10 minutes. When both the product TPD and Alqs are used, a water-cooled stainless steel substrate carrier is used to maintain the substrate turnover to 15C, and the thickness of the AlQ3 layer to be generated. Between 700-n00 Angstroms. After depositing the ΑΙΑ layer, the substrate was removed from the reaction chamber and a Mg: Ag sintered contact was thermally evaporated, and then a protective gold layer of 100 angstroms was evaporated. Using low pressure during deposition can make the organic layer have a smooth and uniform surface. For example, the TPD and A1Q3 layers are measured with an atomic force microscope, and the RMS roughness is divided into 6-8 angstroms and 9-1 丨 angular ribs. The device has a current-voltage characteristic, in which I (XV at low voltage, 1 operation at high voltage ", and the turn-on voltage VT of the power law change related to ^ is about 6 V. Example 2 Use the device of Figure 1 An NL0 film was manufactured, and MT48 was introduced into a 30 cubic centimeter bubbler 46, and its temperature was maintained at approximately 80 by a silicone oil bath 50. -1 00 It was used to generate MT using air bubbles in II gas to carry MT The vapor enters the reaction tube 12 through the glass tube, and the crucible 14 containing the msi at the bottom of the reaction tube 12 is beautifully connected to a position of about 5 cm ^. The pressure of the reaction tube 12 is maintained at about 10_2 Torr. The gas reaction forms a solid film substrate 5 of MST on the substrate 58. The substrate 5 8 is supported by the substrate bottom plate 60, and there is an excess of unreacted mt vapor.

575699 V. Description of the invention (14) is discharged from the exhaust pipe 62, so a DAST film is formed, which can be used in wells such as wells. The invention uses low-pressure deposition technology to produce organic thin films with excellent surface properties and fine composition. Although many specific embodiments of the present invention are described in the text, they are not limited to the specific embodiments.项 技 菽 # Thinking about modifications to the specific embodiment, but still covered by the spirit and ideas of the present invention. 111 The present invention is co-filed with the following patents: "High Reliability, High Efficiency, Integrated Organic Light Emitting Device and Preparation Method", Sequence I ·· n > 0 8/774, 1 1 9 (patent date · 1 99 December 23, 2006); "Multicolor LEd New Materials", Serial Number: 08/85 0, 2 64 (patent date: May 2, 1997); "Electron transport and light based on organic radicals "Launching layer", serial number: 08/7 7 4, 1 20 (patent date: 9 9 December 23, 2006) · "Even ^ display device], serial number: 08 / 772,333 (patent date: 1 9 9 6 December 23, 2009), red light-emitting organic light emitting device (LED) ,, and poor. 〇8 / 774, 〇87 (patent date: December 23, 1996); "Heap ^ has emission Device driving circuit ", serial number: 08/792, 05 0 (patent i date: Π February 3, 1997) 'high efficiency organic light emitting device structure ,, serial number: 08/7 72, 3 32 (patent Date: December 23, 196, "integral, non-polymer elastic organic light-emitting device", 9,319 (patent date: 197 7 y 23rd) II 'and February 3, "Who Tian Shi Xuyi, (patent Issue: February 3, 1997), Bulk Organic Light Emitting Device ,, Sequential Iron · 0 8 / 792,046 (patent date · 1 (^ 7 main 9 = qm "· February 3, 1997);" High Contrast Yes

575699 V. Description of the invention (15) Display of organic light emitting device, serial number: 08/821, 38 0 (patent date: March 20, 1997); "Metal containing 5 ~ hydroxy-line Organic light emitting device with complex as matrix material ", serial number: 08/838, 09 (patent date · August 15, 1997)," light emitting device with high brightness ", serial number : 0 8/844, 3 53 (patent date: April 18, 1997); "organic semiconductor laser 'serial number: 60 / 046,061 (patent date: May 9, 1997);" organic semiconductor laser " Shooting ", serial number: 08 / 859,468 (patent date · May 19, 1997);" saturated full-color stacked organic light emitting device "serial number: 08 / 858,994 (patent date: May 1997 20th); Organic Light Emitting Device Containing Hole Penetration Enhancement Layer ", Serial No. 08 / 865,491 (patent date: May 29, 1997);" Plasma treatment of conductive layer ", Serial No .: PCT / US97 / 1 0 2 52 (Patent date: June 12, 1997; "Manufacture of thin film for organic colorful display devices, in the patent application, serial number · P (: Τ / υ897 / 1〇289 ( Date of the patent · · June 12, 1997); "Infrared light with double heterostructure and longitudinal hole surface emitting organic laser ,, serial number: 6 0/0 5 3, 1 7 6 (patent date: 1 997 7 years 7 May 18); "0LEDs containing a thermally stable asymmetric charge carrier material", serial number: 08/9 ^, 029 (patent date: September 8, 199, 7); "0LED stacking and fluorescent converter Optical fiber laser device 'setting' sequence · 〇8 / 9 25,403 (patent date: September 9, 1997), an improved method for depositing an indium tin oxide layer in an organic light emitting device, , Serial number: 08 / 928,800 (patent date: September 12, 1997); "the alactone-related dopant in the light-emitting layer of OLED,", serial number: 0 8/948, 1 3 0 (patent date: October 9, 1997); "Using a non-metallic cathode high transmission organic light emitting device ,, (patent date · 997 11 575699 V. Description of the invention (16)

May 3), the agent list has the highest transmission of metal cathodes 阴极 ° 20/4 ° (temporary f and "use of non-, organic first-emission devices ,,, (patent date: 丨 9 May 1997) , Agent list number: j 〇〇２〇 / 44, Wang Wen of each co-application patent case is incorporated herein by reference, the proposed inventions and cases US Patent Nos. 08/354, 674, 08 / 613,207, 08 / 632, 322 and 08/693, 359 and the tentative 60 / 010,013, 60 / 024,001, 60 / 025,501 jointly applied for patents, and the full text of each joint application patent is incorporated herein by reference.

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Claims (1)

Volatilize the first organic small molecular substance in the first carrier gas stream; pass the first carrier gas stream through a device, wherein the inner wall of the device is high enough to avoid the condensation effect of the first organic small molecule substance; at 0.001 Torr (Torr) to a pressure of 100 Torr, passing the first carrier gas stream through a substrate; and depositing the first organic small molecule substance on the substrate to form the first organic small molecule substance on the substrate. Of the first film. 2. The method according to item 1 of the scope of patent application, wherein the pressure is from 0.1 Torr to 10 Torr. 3. The method according to item 1 of the patent application scope, wherein the first carrier gas stream is selected from the group consisting of nitrogen, argon, helium, neon, krypton, and xenon. 4. The method according to item 1 of the scope of patent application, wherein the first organic small molecule substance is selected from the group consisting of tris (8-quinoline) aluminum, N, N'-diphenyl-N, N'-bis (3- Tolyl) -1,1'-bisphenyl-4,4'-diamine, α-4,4'-bis [N- (l-naphthyl) -N-phenyl-amine] bisphenyl, 4,4 ', 4Π-reference [N- (3-Tolyl) -N-phenyl-amino] triphenylamine and bis- (8-quinolinyl) aluminophenyl group. 5. The method according to item 1 of the patent application scope, wherein the first film has an RMS surface roughness of less than 11 angstroms. 6. The method according to item 1 of the patent application scope, wherein the first film system comprises N, N′-diphenyl-N, N′-bis (3-tolyl) -1,1′-bisphenyl- 4, O: \ 55 \ 55921-920730.ptc page 24 575699 _ case number 87118943 today # month day amendment _ six, the scope of patent application 4, -diamine. 7. The method according to item 1 of the patent application scope, wherein the method further comprises: volatilizing a second organic small molecule substance in a second carrier gas stream; and blending the second carrier gas stream with the first carrier gas stream; wherein the The deposition step includes depositing the second organic small molecule substance on the substrate, so that the first film includes the first organic small molecule substance and the second organic small molecule substance. 8. The method according to item 7 of the scope of patent application, wherein the pressure is from 0.1 Torr to 10 Torr. 9. The method according to item 7 of the scope of patent application, wherein the first film system is incorporated into an organic light emitting device. 10. The method according to item 1 of the scope of patent application, wherein the method further comprises: volatilizing the third organic small molecule substance in a third carrier gas stream; and applying the third at a pressure of 0.001 torr (torr) to 100 torr. A carrier gas flows through the first film; and the third organic small molecule substance is deposited on the first film to form a second film containing the third organic small molecule substance on the first film. 11. The method according to item 10 of the scope of patent application, wherein the pressure is from 0.1 Torr to 10 Torr. 12. The method according to item 9 of the scope of patent application, wherein the second film is incorporated into an organic light emitting device. 1 3 · The method according to item 9 of the scope of patent application, wherein the second film is a package O: \ 55 \ 55921-920730.ptc Page 25 575699 _ Case No. 87118943 h] Month Day Amendment_ VI. Scope of patent application Contains the (8-quinoline) inscription. 1 4 · A method for manufacturing an organic film, comprising: providing a first carrier gas stream containing one or more volatile first organic small molecule substances; passing the first carrier gas stream through a device, wherein an inner wall of the device is sufficiently high temperature To avoid the condensation of the one or more first organic small molecule substances; exposing the first carrier gas stream to the substrate under a pressure from 0.01 to 100 torr; and depositing the One or more volatile first organic small molecule substances on the substrate to form a first film on the substrate, the first film system comprising one or more volatile first organic small molecule substances; A second carrier gas stream of a plurality of volatile second organic small molecule substances; passing the second carrier gas stream through a device, wherein the inner wall of the device is sufficiently high temperature to avoid condensation of the one or more second organic small molecule substances; The second carrier gas stream is exposed on the first film on the substrate under a pressure from 0. 0 to 1 torr to 100 torr; and the one or more volatile second small organic molecules are deposited. To the first On the film, a second film is formed on the first film of the substrate, and the second film contains one or more volatile second small organic molecules. 15 · The method according to item 14 of the scope of patent application, wherein the one or more volatile first organic small molecule substances include a single first organic small molecule substance O: \ 55 \ 55921-920730.ptc page 26 575699 _ case number 87118943 Q month day amendment _ six, the scope of patent application 'quality. 16 · The method according to item 14 of the scope of patent application, wherein the one or more volatile first organic small molecule substances include two or more first organic small molecule substances. 17. The method according to item 14 of the scope of the patent application, wherein the one or more volatile second organic small molecule substances comprise a single second organic small molecule substance. 18. The method according to item 14 of the scope of patent application, wherein the one or more volatile second organic small molecule substances include two or more second organic small molecule substances. 19. The method according to item 14 of the scope of patent application, wherein the first and second films are incorporated into an organic light emitting device. 20 · The method according to item 19 of the scope of patent application, wherein one of the first and second films is a light emitting layer. 2 1. The method according to item 20 of the scope of patent application, wherein the light emitting layer comprises ginseng (8-quinine) aluminum. 2 2. The method according to item 19 of the scope of patent application, wherein one of the first and second films is a hole transfer layer. 2 3. The method according to item 22 of the scope of patent application, wherein the hole transfer layer system comprises N, N'-diphenyl_N, N'-bis (3-tolyl) -1, Γ-bisbenzene -4,4'-diamine. 24. The method according to item 19 of the scope of patent application, wherein one of the first and second films is a light emitting layer and the other is a hole transfer layer. 25. The method according to item 24 of the scope of patent application, wherein the light emitting layer is O: \ 55 \ 55921-920730.ptc Page 27 575699 _ Case No. 87118943 Amended on the 6th of June _ 6. The scope of the patent application includes ginseng (8-quinoline) aluminum, and the hole transfer layer contains Ν, Ν '- Diphenyl-N, N'-bis (3-tolyl) -1, Γ-bisphenyl-4,4'-diamine. 26. The method according to item 14 of the scope of patent application, wherein the substrate comprises a polymer film material, a glass material or a semiconductor material. 27. The method according to item 14 of the patent application scope, wherein the substrate comprises indium tin oxide. 28. The method according to item 27 of the patent application scope, wherein the substrate is a polyester coated with indium tin oxide. 29. A method for manufacturing an organic film, comprising: providing a carrier gas stream containing one or more volatile first organic small molecule substances; passing the carrier gas stream through a device, wherein an inner wall of the device is sufficiently high-temperature to avoid the Condensation of one or more first small organic molecules; exposing the carrier gas stream to a substrate at a pressure from 0.01 to 100 torr; and depositing the one or more volatiles The first organic small molecule substance is formed on the substrate to form a film on the substrate. The film system includes one or more volatile first organic small molecule substances. 30. The method according to item 29 of the scope of patent application, wherein the film is a light emitting layer. 31. The method according to item 30 of the patent application, wherein the membrane comprises a single first organic small molecule substance. 3 2. The method according to item 30 of the scope of patent application, wherein the film system comprises two O: \ 55 \ 55921-920730.ptc page 28 575699 case number 87118943 VI. Scope of patent application Month Modified or multiple first organic small molecule substances. 3 3. The method according to item 30 of the scope of patent application, wherein the pressure is from 0.1 to 10 torr. 3 4. The method according to item 30 of the scope of patent application, wherein the pressure is from 0.01 torr to 0.1 torr. 35. The method according to item 30 of the scope of patent application, wherein the pressure is from 0.01 to 100 Torr. 36. The method according to item 30 of the scope of patent application, wherein the pressure is from 0.1 Torr to 100 Torr. 37 7. The method according to item 30 of the scope of patent application, wherein the pressure is from 100 Torr to 100 Torr. 38. The method according to item 30 of the scope of patent application, wherein the substrate is cooled. 39. The method according to claim 30, wherein the substrate comprises a polymer film material, a glass material, or a semiconductor material. 40. The method of claim 30, wherein the substrate comprises indium tin oxide. 41. The method according to item 30 of the application, wherein the substrate is a polyacetate coated with indium tin oxide. 42. The method according to item 30 of the scope of patent application, wherein the substrate is a polyester coated with indium tin oxide, which is further coated with a hole transfer layer. 4 3. A device for physically vapor-depositing a film containing organic small molecular substances on a substrate, the device comprising: a deposition reaction chamber; O: \ 55 \ 55921-920730.ptc page 29 575699 _ case number 87118943 amended this year _ month six days _ patent application scope] at least one fluid channel that can exchange fluid with the deposition reaction chamber, the fluid channel contains : (I) the source of carrier gas flow, (ii) the flow of small organic molecules, and (iii) the flow rate controller; a substrate holder placed in the deposition reaction chamber; and fluid exchange with the deposition reaction chamber A vacuum pump is used to provide a pressure of 0.001 torr to 100 torr in the deposition reaction chamber. 4 4. The device according to item 43 of the scope of patent application, wherein the flow rate controller includes a pressure regulator. 4 5. The device according to item 43 of the scope of patent application, wherein the flow rate controller comprises a flow meter. 46. The device according to item 43 of the scope of patent application, wherein the flow rate controller includes an exchange valve. 4 7. The device according to item 43 of the scope of patent application, wherein the deposition reaction chamber has a heating wall. 48. The device according to item 43 of the patent application scope, wherein the deposition reaction chamber has one or more radiant heat sources. 49. The device according to item 43 of the scope of patent application, further comprising a heater substantially surrounding the chamber reaction chamber. 50. The device according to item 49 of the patent application scope, wherein the heater is a multi-zone heater / cooler. 51. The device according to item 43 of the scope of patent application, wherein the substrate holder is cooled. O: \ 55 \ 55921-920730.ptc page 30 575699 _ case number 87118943? Month _ ^ _ VI. Patent application scope 152. The device according to item 51 of the patent application scope, wherein the substrate holder includes a temperature-controlled compartment. 53. The device according to item 43 of the scope of patent application, wherein the source of the organic small molecule substance is an open container containing the organic small molecule substance. 54. The device according to item 53 of the scope of patent application, wherein the open container is heated. 5 5. The device according to item 43 of the patent application scope, wherein the device comprises two or more fluid passages. 56. A device for physically vapor-depositing a film containing organic small molecular substances on a substrate, the device comprising: a chamber reaction chamber; a device for heating the deposition reaction chamber; A device for introducing small molecular vapor into the deposition reaction chamber; a device for cooling a substrate in the deposition reaction chamber; and a device for maintaining a pressure in the deposition reaction chamber from 0.000 to 1 to 100 torr Device within range. 57. A method for manufacturing an organic film, comprising: providing a substrate; providing two or more organic precursor molecules; and placing the organic precursor molecules at a pressure between 10-8 to 10-1 1 Torr And reacting in the presence of the substrate to form the organic film. 5 8. The method according to item 57 of the scope of patent application, wherein the two or more organic precursor molecules are manufactured by bubbling a carrier gas through the organic precursor molecules. O: \ 55 \ 55921-920730.ptc Page 31 575699 _ Case No. 87118943 Q Yue Yue Amendment _ 6, the scope of patent application 1 5 9. According to the method of the scope of patent application No. 57, where the two or more organic first The proton molecule is manufactured by using the organic precursor molecule in a Knuds en element. 60. The method according to item 57 of the scope of patent application, wherein the organic film is a non-linear optical film. 61. The method according to item 60 of the scope of the patent application, wherein one of the organic precursor molecules is selected from the group consisting of 4'-diamidylamine-4-azoin, and sulfur 4'-dimethylamine-4. -Azo azo, 4'-methoxyamine-4-methyl azo stilbene, 4'-dimethylamine-4-ethyl azocarbon and 4'-dimethylamine-4-ethyl A group of methyl azoin hydroxides. 62. The method according to item 60 of the scope of patent application, wherein one of the organic precursor molecules is selected from the group consisting of methyl azostilbene, methanesulfonate, trifluoromethanesulfonate, acetamyltoluenesulfonate, and A group of methyl trifluoroacetate. 6 3. The method according to item 60 of the scope of patent application, wherein the non-linear optical film is selected from the group consisting of 4'-dimethylamine-N-methyl-4-azotoluene tosylate and 4'-dimethylsulfonate Methylamine-4-fluorenylazostilbene, 4'-dimethylamine-4-methylazostilbene trifluoromethanesulfonate, 4'-methoxy-4-methylazosyltoluenesulfonate, A group consisting of 4'-diamidylamine-4-acetamidotoluene tosylate and 4'-dimethylamine-4-methylazostilbene trifluoroacetate. 6 4. The method according to item 57 of the scope of patent application, wherein the organic film is a light transmitting layer. 65. The method according to item 57 of the scope of patent application, wherein the organic film comprises a price-transfer complex. 6 6. The method according to item 65 of the scope of patent application, wherein the two or more are O: \ 55 \ 55921-920730.ptc Page 32 575699 _ Case No. 87118943 Modified on the 6th of June , 7,8,8-tetracyanoquinoline dimethane. 6 7. The method according to item 57 of the patent application, wherein the organic film comprises a guest molecule present in a matrix of a parent molecule. 68. The method according to item 67 of the scope of patent application, wherein the parent molecule is selected from the group consisting of tris (8-quinoline) aluminum and bis- (8-quinoline) aluminobenzene. 6 9. The method according to item 67 of the scope of patent application, wherein the guest molecule is selected from the group consisting of 4- (dicyanomethylene) -2-methyl-6 (p-dimethylamine styryl) -411 _Piran, 5,10,15,20-tetraphenyl-2111, 2311-quine, DCM2, rubberene and coumarin. 70. The method according to item 57 of the scope of patent application, wherein the substrate comprises a polymer film material ' glass material or a semiconductor material. 71. The method according to claim 57 in which the substrate comprises a polyindan oxide layer. 7 2. The method according to item 71 of the scope of patent application, wherein the substrate comprises a polyester coated with polyindan titanium oxide. 7 3. The method according to item 72 of the scope of the patent application, wherein the substrate comprises a polyester coated with poly-indane titanium oxide, which is further coated with a hole transfer layer. 74. The method according to item 57 of the patent application scope, wherein the substrate comprises a hole transfer layer. 7 5. The method according to item 57 of the scope of patent application, wherein the substrate is rotated by 0. O: \ 55 \ 55921-920730.ptc Page 33 575699 Patent Application No. 087118943 Patent replacement page in Chinese (July 1992) 〇